Measurement of dissolved H2, O2, and CO2 in groundwater using passive samplers for gas chromatographic analyses

A simple in-situ passive dissolved gas groundwater sampler, comprised of a short length of silicone tubing attached to a gastight or other syringe, was adapted and tested for in-situ collection of equilibrium gas samples. Sampler retrieval after several days of immersion in groundwater allowed the direct injection of the sample onto a gas chromatograph (GC), simplifying field collection and sample handling over the commonly used "bubble stripping" method for H2 analyses. A GC was modified by sequencing a thermal conductivity (TC) detector followed by a reductive gas (RG) detector so that linear calibration of H2 over the range 0.2-200,000 ppmv was attained using a 0.5-mL gas sample; inclusion of the TC detector allowed the simultaneous quantification of other fixed gases (O2, CO2, He, and Ne) to which the RG detector was not responsive. Uptake kinetics for H2 and He indicated that the passive sampler reached equilibrium within 12 h of immersion in water. Field testing of these passive samplers revealed unusually large equilibrium gas-phase H2 concentrations in groundwater, ranging from 0.1 to 13.9%, by volume, in 11 monitoring wells surrounding four former radiological wastewater disposal ponds at the Y-12 plant in Oak Ridge, Tennessee.     

Pumping-induced ebullition: a unified and simplified method for measuring multiple dissolved gases

The incorporation of multiple dissolved gas measurements in biogeochemical studies remains a difficult and expensive challenge. Incompatibilities in collection, handling, and storage procedures generally force the application of multiple sampling procedures for multiple gases. This paper introduces the concept and application of pumping-induced ebullition (PIE), a unified approach for routine measurement of multiple dissolved gases in natural waters and establishes a new platform for development of in situ real-time dissolved gas monitoring tools. Ebullition (spontaneous formation of bubbles) is induced by pumping a water sample through a narrow-diametertube (a "restrictor") to decrease hydrostatic pressure (PH) below total dissolved gas pressure (PT). Buoyancy is used to trap bubbles within a collection tower where gas accumulates rapidly (1 mL/min) to support multiple chemical analyses. Providing for field collection of an essentially unlimited and unified volume of gas sample, PIE afforded accurate and precise measurements of major (N2, 02, Ar), trace (CO2, N20, CH4) and ultratrace (CFC11, CFC12, CFC113, SF6) dissolved gases in Wisconsin groundwater, revealing interrelationships between denitrification, apparent recharge age-dates, and historical land use. Compared to conventional approaches, PIE eliminates multiple gas-specific sampling methods, reduces data computations, simplifies laboratory instrumentation, and avoids aqueous production and consumption of biogenic gases during sample storage. A lake depth profile for CO2 demonstrates PIE's flexibility as an in situ real-time platform for dissolved gas measurements. The apparent departures of some gases (SF6, H2, N2O, CO2) from solubility equilibrium behavior warrant further confirmation and theoretical investigation.     

Passive sampling and analyses of common dissolved fixed gases in groundwater

An in situ passive sampling and gas chromatographic protocol was developed for analysis of the major and several minor fixed gases (He, Ne, H2, N2, O2, CO, CH4, CO2, and N2O) in groundwater. Using argon carrier gas, a HayeSep DB porous polymer phase, and sequential thermal conductivity and reductive gas detectors, the protocol achieved sufficient separation and sensitivity to measure the mixing ratio of all these gases in a single 0.5 mL gas sample collected in situ, stored, transported, and injected using a gastight syringe. Within 4 days of immersion in groundwater, the simple passive in situ sampler, whether initially filled with He or air, attained an equivalent and constant mixing ratio for five of the seven detected gases. The abundant mixing ratio of N2O, averaging 2.6%, indicated that significant denitrification is likely ongoing within groundwater contaminated with uranium, acidity, nitrate, and organic carbon from a group of four closed radioactive wastewater seepage ponds at the Oak Ridge Field Research Center. Over 1000 passive gas samples from 12 monitoring wells averaged 56% CO2, 32.4% N2, 2.6% O2, 2.6% N2O, 0.21% CH4, 0.093% H2, and 0.025% CO with an average recovery of 95 +/- 14% of the injected gas volume.     

New device and method for flux-proportional sampling of mobile solutes in soil and groundwater

The importance of monitoring the transport of organic contaminants in soil and groundwater, and the pros and cons of existing sampling methods, are outlined. A new, alternative sampling method is proposed, using a passive sampler that functions as a water-permeable, semi-infinite sink for passing solutes of interest. Tracers integrated in the device store information on the volume of water passing through the sampler during the installation period. The conceptual basis of the sampling method is described. This device enables flux-proportional monitoring of the concentrations of mobile contaminants in the soil and groundwater. 14C-labeled phenanthrene (PHEN) and glyphosate (GLY) are used as case study compounds in laboratory experiments. The sorption capacities and uptake kinetics of 13 adsorbents are screened and compared, as well as the dissolution kinetics of three tracer salts: calcium citrate, calcium fluoride (CaF2), and calcium hydrogen phosphate (CaHPO4). The application of the passive sampler is then demonstrated in long-term laboratory experiments, using large soil columns under steady-state hydraulic conditions. The accumulated flux of PHEN was sampled with an accuracy of 3.6%-17.8%, using graphitized carbon, hexagonal mesoporous silica, and cross-linked polymers as adsorbents. The accumulated flux of GLY was sampled with an accuracy of 12.4%, using gamma-alumina as an adsorbent. The advantages and limitations of this new environmental monitoring method are discussed.     

Determination of low levels of methanol and ethanol in licorice extract by large volume injection head-space GC

A large volume injection head-space GC method was established for measuring low levels of residual methanol and ethanol in licorice extract used a food additive. A vial was kept at 50 degrees C in the oven of the head-space sampler. Injection of the head-space gas for 0.75 min into a Poraplot Q GC column with a initial oven temperature of 35 degrees C, enabled the determination of low levels (5 micrograms/g) of methanol and ethanol. The standard deviations for five rounds of analysis of methanol and ethanol in licorice extracts were between 0.82 and 2.97. Methanol was found in 6 samples out of 9 collected in 1999, at concentrations exceeding 50 micrograms/g, the limit set by the Japanese Government, established in 1999 and coming into force on April 1, 2000. The highest concentration reached 10,000 micrograms/g. Methanol at a concentration exceeding 50 micrograms/g was found in 2 out of 9 samples collected in 2000. The highest concentration was 270 micrograms/g.     

Measuring temporal variability in pore-fluid chemistry to assess gas hydrate stability: development of a continuous pore-fluid array

A specialized pore-fluid array (PFA) sampler was designed to collect and store pore fluids to monitor temporal changes of ions and gases in gas hydrate bearing sediments. We tested the hypothesis that pore-fluid chemistry records hydrate formation or decomposition events and reflects local seismic activity. The PFA is a seafloor probe that consists of an interchangeable instrument package that houses OsmoSamplers, long-term pore-fluid samplers, a specialized low-dead volume fluid coupler, and eight sample ports along a 10 m sediment probe shaft. The PFA was deployed at Mississippi Canyon 118, a Gulf of Mexico hydrate site. A 170 day record was acquired from the overlying water and 1.3 m below seafloor (mbsf). Fluids were measured for dissolved chloride, sulfate, and methane concentrations and dissolved inorganic carbon and methane stable carbon and deuterium isotope ratios. Chloride and sulfate did not change significantly over time, suggesting the absence of gas hydrate formation or decomposition events. Over the temporal record, methane concentrations averaged 4 mM at 1.3 mbsf, and methane was thermogenic in origin (delta13C-CH4 = -32.4 +/- 3.4 per thousand). The timing of an anomalous 14 mM methane spike coincided with a nearby earthquake (Mw = 5.8), consistent with the hypothesis that pore-fluid chemistry reflects seismic events.     

A flow-through sampler for semivolatile organic compounds in air

A widely acknowledged limitation of current passive air sampling designs for semivolatile organic chemicals is their relatively low sampling rate, severely constraining the temporal resolution that can be achieved. Addressing the need for an improved sampling design which achieves significantly faster uptake while maintaining the capability of providing quantitative information, a new sampler has been developed that provides greatly increased sampling rates by forcing the wind to blow through the sampling medium. The sampler consists of a horizontally oriented, aerodynamically shaped, stainless steel flow tube mounted on a post with ball bearings, which turns into the wind with the help of vanes. A series of polyurethane foam (PUF) discs with relatively large porosity mounted inside the flow tube serve as the sampling medium. The sampled air volume is calculated from wind speed, which is measured outside the sampler and after passage through the sampling medium using precalibrated vortex rotor and turbine anemometers mounted on top of the sampler and at the exit of the flow tube, respectively. Small battery-operated data loggers are used for data storage. Under typical wind speed conditions, the sampler can collect 100 m(3)/ day, which is approaching the sampling rates of conventional high volume samplers. Controlled experiments in the laboratory and frontal chromatography theory yield the theoretical plate number and breakthrough volumes for polychlorinated biphenyls and polycyclic aromatic hydrocarbons in the PUF plugs and allow for the estimation of breakthrough levels for relatively volatile organic chemicals. After correction for breakthrough, the air concentration obtained with the new flow-through sampler are independent of sampling length and volume and compare favorably with those obtained from conventional pumped high volume samples.     

A water extraction, static headspace sampling, gas chromatographic method to determine MTBE in heating oil and diesel fuel

A method was developed to determine the fuel/water partition coefficient (KMTBE) of methyl tert-butyl ether (MTBE) and then used to determine low parts per million concentrations of MTBE in samples of heating oil and diesel fuel. A special capillary column designed for the separation of MTBE and to prevent coelution and a gas chromatograph equipped with a photoionization detector (PID) were used. MTBE was partitioned from fuel samples into water during an equilibration step. The water samples were then analyzed for MTBE using static headspace sampling followed by GC/PID. A mathematical relationship was derived that allowed a KMTBE value to be calculated by utilizing the fuel/water volume ratios and the corresponding PID signal. KMTBE values were found to range linearly from 3.8 to 10.9 over a temperature range of 5-40 degrees C. This analysis method gave a MDL of 0.7 ppm MTBE in the fuel and a relative average accuracy of +/-15% by comparison with an independent laboratory using purge and trap GC/ MS analysis. MTBE was found in home heating oil in residential tanks and in diesel fuel at service stations throughout the state of Connecticut. The levels of MTBE were found to vary significantly with time. Heating oil and diesel fuel from terminals were also found to contain MTBE. This research suggests thatthe reported widespread contamination of groundwater with MTBE may also be due to heating oil and diesel fuel releases to the environment. used extensively for the past 20 years as a gasoline additive (up to 15 wt %) to reduce automobile carbon monoxide and hydrocarbon emissions. The fact that MTBE is highly soluble in water (approximately 5 wt %) (3) and chemically inert when compared to other fuel constituents causes it to be often detected at high concentrations in groundwater in the vicinity of gasoline spills. The EPA has reported that low levels of MTBE in drinking water (above 40 microg/L) may cause unpleasant taste and odors and has designated MTBE as a possible human carcinogen (4). Past studies have concentrated on the reporting of MTBE levels in groundwater near gasoline spills. Happel et al. reported an MTBE occurrence rate of approximately 78% at locations where hydrocarbons have impacted groundwater (5). Johnson et al. estimate that 9,000 leaking underground fuel tanks have caused MTBE contamination at community water supplies in the 31 states surveyed (excluding California and Texas) (6). Robbins et al. reported finding a significant number of MTBE detections in groundwater samples taken at sites in Connecticut known to be contaminated by heating oil spills (7). Later, this same research group reported finding MTBE contamination to range from 9.7 to 906 mg/L in heating oil and from 74 to 120 mg/L in diesel fuel in samples collected from storage tanks in Connecticut (8). The method used to analyze these samples was based on fuel-water partitioning and GC analysis. This present study provides the detailed basis for that analytical method. MTBE fuel-water partition coefficients as a function of temperature, which are critical to the method, are also presented. This study also reports on variations in MTBE levels as a function of time observed at several residences and a service station. Analytical results are reported for samples taken from terminals as part of an effort to assess the sources of MTBE in heating oil and diesel fuel.     

Pesticide multiresidue analysis of peanuts using automated gel permeation chromatography clean-up/gas chromatography-mass spectrometry

A method based on automated gel permeation chromatography (GPC) and on-line quantitative concentration was developed for the determination of residues of 38 typically used pesticides in high-oil peanuts. Pesticides were extracted using acetonitrile into an oil fraction containing little of the peanut matrix. After changing the solvent to the mobile phase (1 : 1 cyclohexane : ethyl acetate), clean-up was carried out using GPC, the final collected solution being automatically concentrated to a fixed volume and transferred into vials for gas chromatography (GC) injection. The pesticides were analysed by gas chromatography-mass spectrometry (GC/MS) in the selected ion monitoring (SIM) mode. Average recoveries (spiked levels of 0.02, 0.05, and 0.1 µg g^?1) were between 70 and 117%. The relative standard deviation of the method was 3.5–21% (n = 6). This approach gave comparable results with a previously published method.     

毛细管气相色谱法测定肉制品中脱氢乙酸含量

建立肉制品中脱氢乙酸含量的毛细管气相色谱测定方法。该法采用WBI进样口,毛细管色谱柱（弱极性）DB-5（30m×0.53mm,0.5μm）,FID检测器进行检测。进样口温度：250℃;载气流速：10mL/min;程序升温：初始80℃,以10℃/min升至200℃,保持5min;检测器温度：250℃,样品用硫酸溶液酸化无水乙醇定容后直接进样测定。方法简单、快速、重现性好,平均回收率为97.5%,RSD为1.16%,线性范围为10～200μg/mL。     

Estimation of membrane diffusion coefficients and equilibration times for low-density polyethylene passive diffusion samplers

Passive diffusion (PD) samplers offer several potential technical and cost-related advantages, particularly for measuring dissolved gases and volatile organic compounds (VOCs) in groundwater at contaminated sites. Sampler equilibration is a diffusion-type process; therefore, equilibration time is dependent on sampler dimensions, membrane thickness, and the temperature-dependent membrane diffusion coefficient (Dm) for the analyte of interest. Diffusion coefficients for low-density polyethylene membranes were measured for He, Ne, H2, O2, and N2 in laboratory experiments and ranged from 1.1 to 1.9 x 10(-7) cm2 sec(-1) (21 degrees C). Additionally, Dm values for several commonly occurring VOCs were estimated from empirical experimental data previously presented by others (Vroblesky, D. A.; Campbell, T. R. Adv. Environ. Res. 2001, 5(1), 1.), and estimated values ranged from 1.7 to 4.4 x 10(-7) cm2 sec(-1) (21 degrees C). On the basis of these Dm ranges, PD sampler equilibration time is predicted for various sampler dimensions, including dimensions consistent with simple constructed samplers used in this study and commercially available samplers. Additionally, a numerical model is presented that can be used to evaluate PD sampler concentration "lag time" for conditions in which in situ concentrations are temporally variable. The model adequately predicted lag time for laboratory experiments and is used to show that data obtained from appropriately designed PD samplers represent near-instantaneous measurement of in situ concentrations for most field conditions.     

Kinetic gas-water transfer and gas accumulation in porous media during pulsed oxygen sparging

Gas-water mass transfer and the transport of dissolved gases in variably saturated porous media are key processes for in-situ remediation by pulsed gas sparging. In this context, gas dissolution tests were conducted during pulsed oxygen gas injection into sand columns. The columns were recharged with anoxic water, effluents were analyzed for dissolved O2, and tracer tests were performed to detect accumulation of trapped gas. In a second series oxygen gas was blended with sulfur hexafluoride (SF6), and O2 and SF6 breakthrough curves were recorded. To interpret experimental results, a numerical model was applied that simulates multi-species kinetic mass transfer during gas dissolution. The model predicted breakthrough curves of dissolved gas species and delivered spatially resolved values for gas phase accumulation and composition, which are not directly accessible experimentally. It was shown how dissolved nitrogen accumulates increasingly in trapped gas phase and inhibits its complete dissolution, in case the pulsed gas injections were operated based on O2 breakthrough only. Accumulation of nitrogen also retarded dissolved oxygen transport and thus oxygen breakthrough. Experiments plus modeling demonstrated that SF6 measurements are highly sensitive to the gas dissolution processes, and provide a more sensitive criterion for determining gas injection frequencies during pulsed biosparging.     

Novel system for controlled investigation of environmental partitioning of hydrophobic compounds in water

Partitioning behavior of hydrophobic and semivolatile chemicals (such as many POPs and PAHs) in water is key in controlling their environmental distribution and fate. A new equilibrium method is presented here which allows determination of the equilibrium partition coefficient of hexachlorobenzene with suspended particle (K(SPM)≈ 337 L gOC(-1)) in a complex bulk water sample by correcting for a number of sampling artifacts and for the presence of dissolved matter. The method provides simultaneous experimental determination of the fraction of chemical truly dissolved in water (representing in this case about 54% of the bulk water concentration) and that associated to DM (21%). The Henry's law constant was also experimentally determined during the K(SPM) measurements, providing information on the occurrence of partitioning equilibrium in the system for each single observation. Results showed that the high level of quality control and accuracy provided confidence intervals for the K(SPM) estimates within 1 order of magnitude.     

气相色谱法测定蔬菜中三碘苯甲酸残留量

建立三碘苯甲酸残留量的气相色谱测定方法,选取西红柿等6 种基质,样品经0.1mol/L 盐酸酸化,以二氯甲烷为提取剂,超声波提取,用三甲基硅重氮甲烷进行甲酯化,经弗罗里硅土固相萃取柱净化后上机测定,采用电子捕获检测器测定,保留时间定性,外标法定量。并对该方法的灵敏度、准确度和精密度进行实验,三碘苯甲酸的最低检出限可达0.001mg/kg,各水平的添加回收率为70%～95.7%。该方法可靠、灵敏、简便可行,可为制定国家标准分析方法提供参考。     

Field trial and modeling of uptake rates of in situ lipid-free polyethylene membrane passive sampler

Lipid-free polyethylene membrane tubing (LFT) has been further developed in response to a growing need for an inexpensive and simple time-integrative sampling device for dissolved hydrophobic contaminants in water. The LFT sampler is based on the diffusion of dissolved hydrophobic target compounds through the aqueous boundary layer and into the polyethylene membrane, mimicking uptake by organisms. We demonstrate through laboratory and field validation studies that LFT provided the same benefits as many other passive sampling devices, withoutthe potential of analytical interference from lipid impurities. A total of 370 LFTs and semipermeable membrane devices were deployed for 21 days in paired studies at highly urbanized, undeveloped, and two Superfund sites, representing several river conditions. A simple internal surrogate spiking method served as an in situ calibration indicator of the effects of environmental conditions on the uptake rates. A modified extraction method for the LFT increased recoveries while decreasing solvent use and labor compared to other organic extraction procedures. LFT sampling rates were estimated using ratios, in situ calibration and modeling for over 45 target analytes, including PAHs, PCBs, and pesticides.     

Impact of artificial recharge on dissolved noble gases in groundwater in California

Dissolved noble gas concentrations in groundwater can provide valuable information on recharge temperatures and enable 3H-3He age-dating with the use of physically based interpretive models. This study presents a large (905 samples) data set of dissolved noble gas concentrations from drinking water supply wells throughout California, representing a range of physiographic, climatic, and water management conditions. Three common interpretive models (unfractionated air, UA; partial re-equilibration, PR; and closed system equilibrium, CE) produce systematically different recharge temperatures or ages; however, the ability of the different models to fit measured data within measurement uncertainty indicates that goodness-of-fit is not a robust indicator for model appropriateness. Therefore caution is necessary when interpreting model results. Samples from multiple locations contained significantly higher Ne and excess air concentrations than reported in the literature, with maximum excess air tending toward 0.05 cm3 STP g(-1) (deltaNe approximately 400%). Artificial recharge is the most plausible cause of the high excess air concentrations. The ability of artificial recharge to dissolve greater amounts of atmospheric gases has important implications for oxidation-reduction dependent chemical reactions. Measured gas concentration ratios suggest that diffusive degassing may have occurred. Understanding the physical processes controlling gas dissolution during groundwater recharge is critical for optimal management of artificial recharge and for predicting changes in water quality that can occur following artificial recharge.     

Development of a passive sampler to measure personal exposure to gaseous PAHs in community settings

A sensitive, simple, and cost-effective passive sampling methodology was developed to quantify personal exposure to gaseous polycyclic aromatic hydrocarbons (PAHs). A Fan-Lioy passive PAH sampler (FL-PPS) is constructed from 320 sections of 1-cm long SPB-5 GC columns (0.75-mm i.d. and 7-microm film thickness), similar to a mini-honeycomb denuder. Given the unique feature of the GC column stationary phase, gaseous PAHs are collected on the inner surfaces of the columns by molecular diffusion and thermally desorbed to GC/MS for analysis. The sampling rates of FL-PPS were determined in the laboratory using a controlled test atmosphere containing eight PAHs for a range of face velocity, temperature, relative humidity, PAH concentration, and sampling duration. The sampling rate (mean, %RSD, cm3/min) was 26.7 (21%) for acenaphthylene, 37.6 (25%) for acenaphthene, 56.2 (13%) for fluorene, 49.1 (25%) for phenanthrene, 62.7 (22%) for anthracene, 65.4 (24%) for fluoranthene, and 64.4 (18%) for pyrene over a sampling duration of 8-48 h. The sampling rate for naphthalene was approximately 14.1 (12%) cm3/min over a sampling period of 8 h but decreased along with an increase of sampling time. The effects of temperature, humidity, face velocity, and PAH concentration on the sampling rate were not significant for all the compounds tested. A reasonable agreement (<30%) was obtained for most compounds measured by FL-PPS and a conventional active PAH sampling method colocated side-by-side in the field, but a sampling time of 24 h or longer was required for detection of less abundant PAHs in community settings.     

Dissolved gases as partitioning tracers for determination of hydrogeological parameters

In this study, dissolved Kr and SF6 gases were used to determine various hydrogeological parameters of laboratory columns under water-saturated and partially saturated conditions as a function of the flow velocity. The dissolved gases behaved conservatively in saturated columns but were significantly retarded in unsaturated conditions as a direct function of the Henry's law constant (KH) and the ratio of column pore spaces filled with air and water (Vg/Vw). Lower aqueous diffusion coefficients for SF6 compared to that for Kr also resulted in significant rate-limited mass transport across gas-water interface. This effect was exacerbated at higher flow velocities as was indicated by the asymmetric shape of breakthrough curves, more so in the case of SF6. A nonequilibrium advective-dispersive transport model accurately described tracer breakthrough and was used to estimate parameters such as final Vg/Vw under partially saturated conditions and partitioning rates. Internally consistent model results were obtained for both dissolved gases despite the wide range in physical properties (e.g., KH and aqueous diffusion coefficients), suggesting that dissolved Kr and SF6 may be used in conjunction to delineate and validate aquifer characteristics simultaneously from a single pulse injection of the tracer.     

New field method: gas push-pull test for the in-situ quantification of microbial activities in the vadose zone

Quantitative information on microbial processes in the field is important. Here we propose a new field method, the "gas push-pull test" (GPPT) for the in-situ quantification of microbial activities in the vadose zone. To evaluate the new method, we studied microbial methane oxidation above an anaerobic, petroleum-contaminated aquifer. A GPPT consists of the injection of a gas mixture of reactants (e.g., methane, oxygen) and nonreactive tracer gases (e.g., neon, argon) into the vadose zone and the subsequent extraction of the injection gas mixture together with soil air from the same location. Rate constants of gas conversion are calculated from breakthrough curves of extracted reactants and tracers. In agreement with expectations from previously measured gas profiles, we determined first-order rate constants of 0.68 h(-1) at 1.1 m below soil surface and 2.19 h(-1) at 2.7 m, close to the groundwater table. Co-injection of a specific inhibitor (acetylene) for methanotrophs showed that the observed methane consumption was microbially mediated. This was confirmed by increases of stable carbon isotope ratios in methane by up to 42.6 %. In the future, GPPTs should provide useful quantitative information on a range of microbial processes in the vadose zone.     

Field evaluation of a flow-through sampler for measuring pesticides and brominated flame retardants in the arctic atmosphere

A flow-through sampler (FTS) was codeployed with a super high volume active sampler (SHV) between October 2007 and November 2008 to evaluate its ability to determine the ambient concentrations of pesticides and brominated flame retardants in the Canadian High Arctic atmosphere. Nine pesticides and eight flame retardants, including three polybrominated diphenyl ether (PBDE) replacement chemicals, were frequently detected. Atmospheric concentrations determined by the two systems showed good agreement when compared on monthly and annually integrated time scales. Pesticide concentrations were normally within a factor of 3 of each other. The FTS tended to generate higher PBDE concentrations than the SHV presumably because of the entrainment of blowing snow/ice crystals or large particles. Taking into account uncertainties in analytical bias, sample volume, and breakthrough estimations, the FTS is shown to be a reliable and cost-effective method, which derives seasonally variable concentrations of semivolatile organic trace compounds at extremely remote locations that are comparable to those obtained by conventional high volume air sampling. Moreover, the large sampling volumes captured by the FTS make it suitable for the screening of new and emerging chemicals in the remote atmosphere where concentrations are usually low.